Epihalohydrin reaction products of phosphorous and sulfur oxygen acids and amines



United States Patent 3,304,349 EPIHALOHYDRIN REACTION PRODUCTS OF PHOSPHOROUS AND SULFUR OXYGEN ACIDS AND AMINES Kwan-Ting Shen, St. Louis, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Filed Dec. 12, 1962, Ser. No. 244,020 2 Claims. (Cl. 260-920) This invention relates to the reaction products of (1) an epihalohydrin, (2) an anionic compound capable of reacting with the epoxide group of the epihalohydrin, and (3) an amine or an analogous compound thereto, for example sulfur, phosphorous, etc. analogues of an amine. These reaction products will also be referred to herein as epihalohydrin reaction products.

Probable products may be illustrated by the following:

X is halogen, A is an anionic group and B represents an amine or an analogue thereof, i.e. a cation.

, As seen above, the epoxy ring opens, and the halogen reacts with the amine.

For convenience these epihalohydrin reaction products may be expressed by the formula:

R where .A is derived from any anionic compound contain- 1 ing a hydrogen atom which is capable of reacting with the epoxide group of the epihalohydrin, for example, a

salt of the following:

(1) An acid of sulfur and oxygen, for example, sulfuric,

, sulfurous acids, etc., hydrosulfiuric, hydrosulfur'os, etc.

acids, and the like. i t

(2) An acid of phosphoros and oxygen, for example phosphoric, phosphorous, pyrophosphoric, polyphosphoric, etc., acids.

(3) Arninomonocarboxylic acids, for examle of the formula where R is hydrogen or a substituted group, for example i it alkyl, aryl, aralkyl, alkaryl, etc. R' is .al'kylene, arylene,

alkarylalkylene, etc. -R may be [for example CH iCH l n=0-2O or higher,

etc.; R may be (CH l where n=l-20 or higher,

etc

(4) Amine dicanboxylic acids 0 ENG/i OH):

3,304,349 Patented Feb. 14, 1967 where R has the same meaning as above, for example,

0 HHKCHmi J OH], etc.

(5 Amino sulfur-oxygen acids H OHaN(CHz)aSOaH NH (CH SO H, etc. where R and R have the same meaning as above.

(6) Hydroxy carboxylic acids (including phenolic acids) O (HO)nR[ii 01111:

Where R=alkylene, arylene, alkarylalkylene, etc, n=l-6 or higher, but preferably 1, m: 1-3 or higher, but preferably 1, for example sugar acids, for example such as saccharic acid, etc.,

ll HO(CH1)1-mi'iOH, etc., HO(OH:)2C OH O 0 ll L L HO OOH, HO CH1 OH (7) Hydroxy sulfur-oxygen acids '(including phenolic acids) (nouneona --SO4H where R, n and m have the same meaning as for the hydroxy carboxylic acids, for example HO(CH SO H, HO(CH2)110SO4H,

HOG-801E etc.

(8) Sulfur analogues of hydroxy acids, for example (HS) R{-SO H] (HS) lR-ESO H] (HSLIR [:11]. (HS n [SmHlu for example 1 10SO3H, 1 10SO4H etc.

(9) Miscellaneous anionic materials such as salts of arsenatcs, borates, tartrates, etc.

B is derived from any amine capable of reacting with the halo group so as to be chemically bonded to the CH group including monoamines, polyamines, hydroxylamines, oxyalkylated amines, etc. The amine may be primary, secondary or tertiary, but preferably tertiary. B can also form salts with the anionic moiety of the molecule, for example The following are examples of amines which can be employed in this invention.

I. MONOAMINES A. PRIMARY MONOAMINES These include compounds of the formula RNH where R is a substituted group preferably a hydrocarbon group, for example alkyl, cycloalkyl, aryl, alkenyl, heterocyclic, substituted derivatives of the above, etc.

Alkyl Alkyl includes methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl, etc. having 1-50 or more carbons, such as 1-30, but preferably 1-18 carbons.

The term alkyl also includes isomers of the straight chain group wherein branching occurs along the chain, for example These include furyl, pyranyl, hydrogenated furyl, pyranyl, etc. groups.

B. SECONDARY AMINES These include amines of the formula RN- H where R and R, which may or may not be the same, have the same meaning as stated above, for example dimethyl amine, diethyl amine, dipropyl amine, diamylamine, dihexyl amine, dioctyl amine, didodecyl amine, dihexyldecyl amine, etc., methyl ethyl amine, methyl octyl amine, butyl octylamine, methyl octadecyl amine, etc.; methyl octa decenyl amine, dioctadecenyl amine, etc.; dicyclohexyl amine, methyl cyclohexyl amine, etc.; methyl furyl amine, methyl benzyl amine.

C. TERTIARY AMINES These include amines of the formula where the Rs, which may or may not be the same, have the same meaning as stated above, for example, trimethyl amine, triethyl amine, dimethyl octyl, dimethyl dodecyl, dimethyl tetradecyl, diethyl hexadecyl, methyl ethyl octadecyl dimethyl octadecyl, etc., dimethyl octadecenyl, diethyl hexadecenyl, etc. dodecyl benzyl methyl, decyl dibenzyl, etc., dimethyl furyl, etc., dimethyl phenyl, diethyl naphthyl, etc., dicyclohexyl methyl, dimethyl cyclohexyl, etc.

D. COMMERCIAL AMrNEs Representative commercial amines are available, for example, these shown in the following table.

The nomenclature of these amines is derived from either their chain length or source of raw material, for example,

Armeen 8D Octyl amine.

Armeen C Coconut oil amine.

Armeen S Soybean oil amine.

Armeen T Tallow amine.

Armeen O Oleyl amine.

Armeen HT Hydrogenated tallow amine. Armeen DMCD Dimethylhydrogenated coco amine. Armeen M2HT Dialkylhydrogenated tallow amine.

Products with D designate distilled grade. Without D designate technical grade.

A preferred amine is a di-lower alkyl 7 carbons) mono-higher alkyl (8 or more carbons, such as 8-20 or more, but preferably 10-18 carbons).

Products TABLEI Primary Second- Diamines ary NlklCl 21 1 Q Q Q Q ea Q Q g Q -a min 1a 00 E y Lengfi. saaaammaaeem oe ii g EEEE sasasae eaaaaeaaaasag Q2 1 QQQQ Tetradeeyl Hexadecyl OctadecyL Octadeeeny1 Octadecadienyl M01 combining wt 135 166 213 195 227 250 300 275 300 280 298 274 297 275 223 208 450 530 321 310 402 400 PercentPrimaryAmine 82 94 92 85 95 85 95 85 95 86 95 .85 95 40 44 40 40, Percent SecondaryAmine 85 85 Approx. Melting Pt.,C 13 8 24 24 29 38 57 55 55 46 41 31 22 24 21 46 68 22 20 40 Co10r,FAC 339333113113113197113951911131a Grnde DD'IDDDTD'ID'IDIDIDDDTDI'1 The dimethyl tertiary amines oi the above would be represented by a DM prefix. Thus, dimethyl Armeen 8D would be Armeen DM8.D and;

dimethyl Armeen 12 would. be Armeen DM12, etc.

TABLE II Dimethyl Tertiary Amine Dialkyl Tertiary Amines a a a a 5 Carbon Q N-Alkyl Chain Chain 3 S 2 E o o m 0) ta m g 0 m Length 2 2 E 2 2 2 2 2 2 2 N N or Q Q Q Q Q Q Q Q Q Q 2 2 S a a a a a a a a B a a a a 4 Q Q 1 1 3 Q 1 4 1 14 2 2 2 Hexadecyl 16 92 92 6 6 8 8 20 24 24 24 s 20 Octadecyl 1s 7 7 90 90 5 5 17 17 71 71 71 5 17 Octadecenyl 1S 1 1 4 4 5 5 26 26 3 3 3 5 26 Octadecadienyl l8 37 37 37 M01. weight, theoretical 271 7 295 295 2 224 289 289 289 289 522 389 520 M01. combining weight 338 295 869 321 280 224 361 314 361 314 564 436 594 Percent Tertiary Amine. 80 9 80 92 80 92 80 92 80 92 Approx. Melting Pt., C 12 1(1) 2% 2(1) 1g 1g 18 -21! 1g 7 I? 28 --5 9 c 1 G d e ,1933 Ggage f ifj T D T D T D T D '1 D T T T 1 D-Distillcd, T-Teclmical.

Other commercial amines include the following: 30 II. POLYAMINES Primene amines CH CH These include polyammes corresponding to the formula RI! RI! OE:- --CH2 -NH1 i..\ in. RI! RI! ROSIII Amine D GENE, x=0 to 8 or greater, in which R" (which may or may not I I be the same) is hydrogen, alkyl, cycloalkyl, aryl, or aralkyl and R is a divalent radical such as CH CH CH CH CH H -c-cm, -om 3rrom, -o11( 1n-, CHOH-(|3H- F H: CH; hm on, :11, on. CH:

etc. etc. I i Ethylenediamine,

E. CYCLIC SECONDARY AND TERTIARY AMINES Diethylenetriamine, Also included within the definition of secondary and g il i g tertiary amines are those amines where two of the R l P P groups are joined in a cyclic structure such as ene P g R Dipropylenetriamme, x Tripropylenetetramine, EN RN Butylenediamine,

M 5 Aminoethylpropylenediamine,

Examples of these amines include pyridine, quinoline, isoquinoline, acridine, piperidine, piperazine, morpholine, etc., certain N-substituted derivatives thereof, such as N-alkyl morpholine; N-alkyl piperidine, N-alkyl piperazine, etc. for example N-dodecylmorpholine, N-octadecylmorpholine, N-dodecylbenzylpropholine, N-nonylmethylbenzylmorpholine, N-cetylpiperidine, i Octylphenoxyethoxyethylmorpholine, Nonylphenoxyethoxyethylpiperidine,

Aminoethylbutylenediamine,

Other polyamines in which the nitrogen atoms are separated by a carbon atom chain having 4 or more carbon atoms include the following: Tetramethylenediamine, pentarnethylenediamine, and especially hexamethylenediamine.

Another class of polyamines which may be employed are those sold under the trademark Duomeen which is a designation for certain diamines. Duomeen amines have the following general formula:

H R-N-CHr-C Hr-CHz-NH:

R is an 'alkyl group derived from a fatty acid or from the mixed fatty acids as obtained from certain oils. The specific Duomeen and the source of the radical R are as follows:

( 1) Duomeen 12, R=lauric,

(2) Duomeen C, R=coconut oil fatty acid,

(3) Similarly, a comparable diamine, obtained from Rosin Amine D and acrylonitrile, can be prepared.

ILIC CHzNH-CHaCHqCHaNI-Iz H /CH3 p C H Additional examples of polyamines include the following:

H C aHnNC H20 HFNHB N-ootyl ethylenediamine H C iuHsa-N-O Hr C Hr-NH:

.N-hexadecylethylenediamine .H H H C12H25 NC2H4NCZH4 NCEH4'NHI N dodecyl triethylenetetramine H C12H25NC sHu-NH:

fN-d'odecyl propylenediamlne Diamines containing tertiary amino groups for example 02H! H C 12H25N-C sHaN- C 2H5 It is to be noted that the above examples show high molal groups, i.e., 8 carbon atoms or more. The same derivatives in which methyl, ethyl, propyl, butyl, amyl, hexyl groups, or the like, appear instead of octyl, decyl, etc., are equally satisfactory.

Acylated polyamines can also be employed, for example:

H H ll H NHrOiH|N-O-dlmerlc-C-NCzHaNH:

etc.

Although the formula of the epihalohydrin reaction products may be expressed as a-orn-on-omfi compositions containing multiple units can also be formed. For example where the anion is AH and both Hs react, a possible formula is e 29 e BCH1'CH-CH2ACH2?H-CH2-B OH OH Similarly, Where B is a diamine, a possible formula is In addition, epihalohydrin reaction products may have plural units because of plural active hydrogen associated with AH and plural amino groups associated with the polyamines, for example a polymeric structure containing plural units of the following structure Other structures will be evident to those skilled in the art.

It should be understood that the formulae expressed herein are representations of probable products formed and that other products or mixtures of products can also be formed. Therefore, the products may be best expressed as reaction products of (1) an epihalohydrin, (2) an anionic compound containing a hydrogen atom capable of reacting with the epoxide group of the epihalohydrin, and (3) an amine or an analogous compound thereto, for example, the sulfur, phosphorus, etc., analogues of amines rather than by any specific formula.

, Illustrative examples include the following:

Z is derived from dimeric acid (C In the above formulae R, R", R', R" are hydrogen or a substituted group such as alkyl.

The reactions are generally carried out as follows: The metal salt of the anionic material is first dissolved in water, by warming if necessary. Epichlorohydrin is added to the clear solution. The reaction mixture is heated until a clear solution is obtained. To clear this solution is then added the amine or an analogous compound. Heating is applied until the reaction mixture becomes clear again. Dry products are obtained by evaporating off the water. i

The following examples are presented for purposes of illustration and not of limitation.

Example 1 G. Sodium bisulfite (0.1 mole) 10.4 Water 41.0 Epichlorohydrin (0.1 mole) 9.3 Dimethyl dodecylamine (0.1 mole) 21.3

Sodium bisulfite was dissolved in water. Epichlorohydrin was added to the clear solution. The reaction 10 mixture was heated for one hour and became clear at about C. The tertiary amine was added slowly. The turbid mixture was then heated to reflux. The heating lasted about two hours until the reaction mixture became clear.

Example 2 G. Sodium bisulfite (0.1 mole) 10.4 Water 51.8 Epichlorohydrin (0.1 mole) 9.3 Octylphenoxyethoxyethyl dimethylamiue (0.1

mole) 32.1

The reaction was carried was carried out as in Exam- Epichlorohydrin was added to an aqueous solution of the sodium salt. The mixture was heated for 15 minutes. A clear solution was obtained at about 55C. The tertiary amine was added. The turbid solution was heated at reflux for 20 hours until it became clear.

Example 5 G. Sodium isothionate (0.1 mole) 14.8 Water 48.2 Sodium hydroxide 0.5 Epichlorohydrin (0.1 mole) 9.3 Armeen DMl4D (0.1 mole) 24.1

Sodium isothionate and NaOH were dissolved in water. To this clear solution was added epichlorohydrin with heating. The mixture became clear after about three hours. The final temperature was 96 C. The amine was then added. The reaction mixture was refluxed for one hour to give a clear yellow solution.

Example 6 Sodium gluconate (0.1 mole) 21.8 Water 55.2

NaOH 0.5 Epichlorohydrin (0.1 mole) 9.3 Armeen DM14D (0.1 mole) 24.1

Sodium gluconate and NaOH were dissolved in water.

To the clear solution was added epichlorohydrin and heat was applied to the mixture which became clear after one hour. The final temperature was about 65 C. The amine was added and heating continued for another hour at reflux. The final product was a brown thick clear solution.

Example 7 G. Phosphoric acid (0.05 mole) 5.8 Water 45.0 Epichlorohydrin (0.05 mole) 4.6 Armeen DM14D (0.15 mole) 36.2

Epichlorohydrin was added to the aqueous solution of phosphoric acid. Heating was applied for 15 minutes. The mixture became clear at 60 C. The amine was added slowly and heating continued for three hours at reflux. The final product was a clear thick solution.

Example 8 G. 5 Sodium N-coco-fi-amino propionate (0.1 mole) 27.2 Water 84.2 Epichlormohydrin (0.1 mole) 9.3 Triethylene diamine (0.05 mole) 5.6

Sodium N-coco-fi-amino propionate was dissolved in 10 hot water. To the clear solution epichlorohydrin was .added drop-wise. The milky solution was then heated for half an hour at reflux. The amine was added and heating continued for one hour. The final product was very thick. 15

12 Example 9 G. Sodium bisulfite (0.1 mole) 10.4 Water 51.8 Epichlorohydrin (0.1 mole) 9.3

TABLE IIL-EPIHALOHYDRIN REACTION PRODUCTS FORMED BY REACTING (1) WITH EPICHLOROHYDRIN AND THEN WITH (II) (EQUIMOLAR AMOUNTS) Ex. Anionic Reactant (I) Cationic (II) Reaetant 10 NaHSOz Armeen DM16D,

11 NQHSO; Armeen DM18D.

12 KH2PO4 Armeen DM14D.

13 KHzPO4 Armeen DM16D.

14 KH2PO4 Armeen DM18D.

CHzC O ONa 15 IIN\ Anneen DM14D.

OHIO O ONa CHzC O ONa 16 HN\ Armeen DM16D.

CHzC 0 ON&

CHzC O ONa 17 HN Armeen DM18D.

CIhO O 0N2 CHzC OONa H (I? 18 HN C1:H |-C-C\ $111 CHgCOONa NCI'I1CH:CH;N-CH;

CH3-C O H H CnHn-CC\ (RH; 19 NaHSO: NCHCH CHgN-CH] CHr-(fi 0 H H C1:HaC-C\ (I311: 20 KHzPOt NCH:CH1CH1NCH:

CH -(fi 0 21 NaHSOa /NH CH3 1 CH 22.. NaHSOn /NH 23 KHzP04 N-CH:

Pyrophosphoric acid O O noi oi -oi -on )H OH Tripolyphosphorie acid (1) Phosphates having ring-like anions such as found in the meta phosphates, for example i Trimetaphosphoric acid TABLE III- C0ntinued Ex. Anionic Reactant (I) Cationic (II) Reaetant 24 KH2PO4 N-CH5 25 KHzPO Tetrarnethyl dimer diarnine.

C H\z 26 Sodium N-Coco-fl-Aminopropionate N-CH:

CH, CI\*I\2 27.- l0 I NH 28 Sodium N-Coeo-fl-Aminopropionate Tris-hydroxymethyl Amino Methane. 29 .(lo N-methyl glueamine.

30.. do /NCH:CI-IzOCI-I2CH2OH 31 Sodium bitartrate (NaHC4H4OsH1O) Armeen DM12D. 32 Sodium cellulose sulfate Armeen DM12D. 33- do Armeen DMCD. 34-. dn Arrneen DM14D.

Polyphosphates 0 on One class of anionic compounds capable of reacting 35 {l with epihalohydrin in accord with this invention are the O condensed phosphates. In general, a condensed phosphate embracesa group of pentavalent phosphorous com- I pound in which various numbers of P0 groups are H0 0 P linked together by oxygen bridges.

The structures of individual phosphoric acids found in polyphosphates include the following: 0 O

O Tetrametaphosphorlc acid H 0 0 o o HO-POH H H H II I! 0H -OPO-1[O1|O 1 o1 o1 o Orthophosphoric acid OH OH OH OH OH 0 0 Linear meta and poly- O=POH H II phosphates HO.POP OH 0H Ultra or crosslinked on OH phosphates All three groups come under the heading of condensed phosphate for the simplest method for their preparation is still by condensation reactions by elimination of water It is also common to condensed phosphates that, on appropriate treatment with water, they are hydrolytically broken down to orthoor mono-phosphates, usually by a series of intermediate reactions.

All phosphates can be represented stoichiometrically as combinations of oxides. Thus, Na HPO can be written as 2Na O-H O-P O and Na P O as 5NaO-3P O The ratio (R) of cationic oxides (such as Na O and CaO and including H O of composition) to anionic oxides (P O determines the type of phosphate. If the mole ratio of cationic to anionic oxide, for example (NaO+H O+CaO)/P O is 3, the substance is an orthophosphate. If it lies between 1 and 2, the substance is a polyphosphate and in a pyrophosphate (dipolyphosphate) the ratio is exactly 2. A ratio of exact unity gives 75 p a metaphosphate. If the ratio lies between 0 and unity,

the substance is an ultra or cross-linked phosphate. This relationship is illustrated in the following table:

Although salts are employed, these contain suflicient active hydrogen due to hydrolysis to react with the epox- TABLE IV.CLASSIFICATION OF PHOSPHATES Oxide ratio, R Name General formula of Normal Sodium Salt Structures eluding double salts and solid solutions).

P40 0 molecules or continuousstruetlros. Interconnected chains and/or rings.

Rings (or extremely long chains).

Chains. Two phosphorous atoms.

One phosphorous atom.

Analogous compound within the scope of this invention can also be prepared by condensed arsenates and conide group, i.e. the active hydrogens may be formed in situ. In addition, the epoxide group of the epihalohydrin densed arsenate phosphates 20 can react with salts such as salts of carboxylic acids g o OH 0 on ol .s O1I\s o- OH OH n l /O 1 /O 0 0 o l! O l 0 ll 0 ll f T o 0 on o 0 0H OH OH 9 OH OH etc. so as to form Unlts of the followlng in various arrangements 0 ll oi or -o [-o-i' 0iiso-1b *0 RONa sNa OH OH OH OH g H H -OOOH1CH-CHqCl, -ROCHzCI-IOH;O1 0 M o nfi OH OH em oomonomo1 Meta arsenate-phosphates in variations of the follow- ()Na ing units etc. groups.

K 40 Ester of polybasic inorganic acids and hydroxylated As P materials, particularly polyols and their metal salts can H0 O HO 0 also be reacted as anionic materials according to this \i A% L invention. Examples of polybasic inorgani acids inelude sulfuric acid, phosphoric acid, arsenic acid, etc. 0 0 0H 0 O OH Examples of polyols include glycols, glycerols, sugar aland the like. cohols, cellulose, ox yalkylated polyols, oxyalkylated In addition to polyphosphates, polyarsenates, etc., one may employ in an analogous manner polyborates and poly compounds containing mixed units of those stated above.

phenol-formaldehyde resins, etc.

The reactions were carried out in the same way as described above. Examples were presented in the following table:

TABLE V.PRODUCTS FORMED BY REACTING (I) WITH ONE MOLE OF EPIOI-ILOROHY DRIN AND THEN WITH (II) Ex. Anion (I) Moles Cationic Reactant (II) Moles N 414F20 (Tetrasodium pyrophosphate) 1 Armeen DM12D 1 Namom (Sodium tripolyphosphate) d 1 NaaPnOm (OllfOS) 1 N amPnOn (Sodium hexametaphosphate) 1 N agB4O7.10H O (Borax) 1 (EH-(3H2 (.llHa N N-OH2CHNH:

7 NflltPuOn O. 1 Armeen DMMD 1 8 NamPgO a 0. 1 UHF-0H2 1 N N-OHaOHzNH f CuHaa 0. 2 Armeen DM14D 1 0.2 CmH NHCHZCHZCI hNH 1 0.2 C12H25NHCH2OI'I2CH2NH2. 1 0. 2 C1iH NI-I2 1 1 C1sHa5NHz 1 17 The ratio of polyphosphates, etc. to epichlorohydrin can vary from one to one to one to n, where n=number or potassium atoms in the molecule.

Oxyalkylation Since the epihalohydrin reaction products of this invention contain hydroxy groups, they can be oxyalkylated in any suitable manner with any suitable a,fi-alkylene oxide, for example, alkylene oxides of the formula:

Equivalents of alkylene oxides can also be employed, for example alkylene carbonates, i.e. ethylene carbonate, propylene carbonate, butylene carbonate, etc. In addition alkylene oxides of the glycide, methyl gly-cide, etc. type and their equivalents can also be employed.

Furthermore, (AO),,- denotes (1) homo units for example (EtO) (PrO) (BuO) y )n etc., (2) block units, (EtO) -(PrO) etc. where a-l-b+c=n; (3) heteric units containing random mixtures of more than one oxide --(EtO-PrO) (PrO-BuO) (EtOBuO) wherein the ratio of each oxide to the other is for example 199 to 994; (4) heteric-homo block units for example (EtOPrO),,-(BuO) etc. where EtO-, PrO-, BuO are units derived from ethylene, propylene, and butylene oxides respectively.

-(OA),,- can also be derived from an oxetane (e.g., a,'y-'alkylene oxides), for example those of the formula where E and D are hydrogen or a substituted radical, for example alkyl, aryl, cycloalkyl, alkenyl, aralkyl, etc.

In addition E and D can be substituted, such as where the oxetane is derived from pentaerythritol and derivatives thereof. Examples of such oxetanes can be found in the American Chemical Society Monogram The Pentaerythritols by Berlow et al. (Reinhold 1958), chapter X.

18 Preferred embodiments of such pentaerythritol derived oxetanes include those of the formula where X and Y are halogen, cyano, hydroxy and alkoxy.

Since the products of this invention may be block polymers containing blocks or segments of alkylene oxide units which are added sequentially, oxyalkylation is in essence a step-wise procedure. For the sake of simplicity of presentation, the invention will be illustrated by employing as a base oxyalkylatable epihalohydrin reaction product Q(OH) and by employing only ethylene, propylene, and butylene oxides with the understanding that other hydrophobe oxides (i.e. other than ethylene oxide) can be used in place of propylene and butylene oxides such as amylene oxide, octylene oxide, styrene oxide, oxetanes, etc. These are shown in the following Table where Q(OH) is the epihalohydrin reaction product having OH groups.

(MO=mixture of EtO-PrO for example 1:1, 3:2, 223, etc. molar ratio) Step II Reaction of the Step I product with one of the five oxides or mixtures employed in Step I, which oxide had not been reacted in the immediately preceding step, to give for example:

Step III The products of Step II can be reacted with one of the five epoxides or mixture of oxides which had not been reacted in the immediately preceding step, i.e. either EtO, PrO, BuO, MO, or PrOBuO, with the above exclusion as to the epoxide just reacted. This will be illustrated as follows:

Step IV involves the oxyalkylation of the products of Step III. Step V involves the oxyalkylation of Step IV. Further oxyalkylations involve Steps VIX or higher. This process can be continued ad infinitum.

Depending on the particular application, one may combine a large or small amount of alkylene oxide. Thus, one may combine the alkylene oxide to the epihalohydrin reaction product in mole ratios of 1:1 or less to l000:1 or more such as 1l00, for example 1-50, but preferably 120. However, it should be understood that the preferred ratio will vary as to the particular application, the particular alkylene oxide, the particular ratios of the oxide, etc.

Sulfur analogues of the alkylene oxides can also be employed. 7 Thus, Q(OI-l), can be oxyalkylated with alkylene oxide, alkylene sulfide, or mixtures of alkylene oxides and alkylene sulfide in a random or block-Wise fashion. The following compounds are exemplary:

cidyl phenyl ether, etc., glycidyl amine such as glycidyl dialkyl amino methane of the formula 111 oH2- -oHoHiN when R+R are alkyl groups, etc.

(3) Alkylene imines such as ethylene imine, propyleneimine, higher alkyleneimines.

(4) Alcohols or otheir equivalent, such as alkyl sulfate, alkyl halides, etc. to form others.

2t) (5) Esters prepared from monocarboxyl acid as acetic, benzoic, etc., acid, for example an acid of the formula M 2-0 on;

where Z comprises a saturated or unsaturated alkyl radical, a cycloalkyl radical or an aromatic radical. The polycarboxyl esters may be full esters or fractional esters, i.e. where the free carboxylic acid group is present in the molecule.

Polycarboxylic acid can advantageously be employed and its structure can be varied widely. In general, they Can be cXpreSSed aS Z O OI'I x where Z comprises a saturated or unsaturated aliphatic radical, acycloaliphatic radical, an aromatic radical, and the like, and x is a whole number equal to 2 or more, for example, 2-4, but preferably 2.

Examples of the polycarboxylic acids comprise those of the aliphatic series, for example, oxalic, malonic, suc cinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, unclecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids comprise furnaric, rna'leic, mesaconic, citraconic, itaconic, muconic, aconitic acids, and the like.

Examples of aromatic polycarboxylic acids comprise phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc. derivatives), biphenyldicarboxylic acid, diphenylether di carboxylic acids, diphenylsulfone dicanboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two carboxylic groups comprise hemimellitic, tri mellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polycarboxylic acids comprise the dimeric, tri meric and other polyacids, for example, dilinoleic acid, trilinoleic acid, polylinoleic acid, and the like such as those prepared by Emery Industries. Other polycarboxylic acids comprise those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as esters, anhydrides, glycerides, etc. can be employed in place of the free acid.

In summary, the products of this invention include the reaction products of (1) an epihalohydrin, (2) an anionic compound capable of reaction with the epoxide group of the epihalohydrin, and (3) an amine or analogous compound thereof. These products are best expressed by the process of manufacture since the reaction products may form many possible reaction products. For example with an amino acid O i i- 'i-o-@ each of the encircled Hs could react with the epoxide group or the sodium salt of the amino acid,

could react with the halogen atom of the epihalohydrin. Thus, mixtures are probably formed in allreactions. One possible product has a dipolar structure.

A om- :Hom-B OH and the like. A preferred embodiment is to employ a po'lyphosphate salt as the anionic material. The preferred amino reactant'is a tertiary amine.

Equivalents may also be employed. For example may be reacted with the anionic material. Since epihalohydrin reaction products contain an OH group, they can be reacted at this position by oxyalkylation, acylation, etc. or by any other reactant capable of reacting with an OH group. Analogues and closely related compounds can also be employed for example,

XCHr-CH-OH-CH1X so as to form compounds of the type B-CHr-CH-CH-CHz-X h on etc., as well as employing sulfur, phosphorus, etc. analogues of amines.

Uses

The compositions of this invention may be employed as follows:

(1) As surfactants, detergents, dispersants, wetting agents, etc.

(2) As cleaning agents for (1) soft surfaces such as textiles, cotton, wool, rayon, synthetic fibers, etc. and (2) hard surfaces such as metal, glass, ceramic, painted, plastic, linoleum, etc. surfaces.

(3) In textile industries in such operation as (a) Dyeing, for example in dye levelling,

(b) Wetting (c) Emulsifying (d) Lubrication to facilitate spinning, weaving, and

knitting.

(4) In dry cleaning, for example, to remove water soluble materials.

(5) In flotation and benefication of ores, for examples as collectors and/ or promotors.

(6) In electroplating and the suface finishing of metals.

(7) As cutting and fabricating lubricants, for example, in cutting oils, drawing and rolling lubricants, etc.

(8) In asphalts, for example as anti-stripping agents, in asphalt emulsions, etc.

(9) In cement and concrete, for example to improve the plasticity, workability and fluidity of concrete slurries, to improve free-thaw resistance, to waterproofing concrete and masonry, as air entraining agents, etc.

(10) In agricultural uses, for example to reduce caking, to prepare emulsions of insecticides, fungicides, herbicides, etc.

(11) In processing leather and furs in salting, soaking, scouring, fieshing, tanning, bleaching, dyeing, fat-liquoring or oil finishing, etc. operations.

(12) In the paper industry and in the processing of viscose.

(13) In emulsion polymerization of synthetic rubber and polymers, for example in dispersing the prepolymerized materials in water or other liquid media, in creaming natural latex, the formation of plastic foam, in bonding polymers to fabrics and other materials, the dispersion of fillers and pigments into polymers, etc.

(a) In drilling muds as emulsifiers.

(b) As a wetting agent in primary production. (c) In air drilling as foamer, desander, etc. (d) To remove mud, wax, etc. from well bore.

(16) In secondary oil recovery (1) As Wetting agents for acid treating and hydraulic fracturing.

(2) In water flooding to effect preferential wetting.

(17) As a demulsifier for petroleum for both W/O and O/W emulsions.

(18) As corrosion inhibitors.

(19) As scale inhibitors.

(20) As antiseptic, preservative, bactericidal, bacteriostat germicidal, fungicidal agents.

(21) As additives for fuel oil, for example as detergents, sludge-suspending agents, etc.

(22) As foaming agents, for example, in fire fighting foams, in air drilling, in desanding walls, in gas-lift Wells.

(23) As general emulsifying agents for example in cosmetics, agricultural, paint, coating, flavoring oil, perfume oil, asphalt and bitumen, furniture and floor polishes, etc.

(24) As chelating agents.

(25) As anti-static agents.

(26) As deinking agents for printed material such as newspapers, etc.

(27) As flocculants, for example, in water purification,

etc.

(28) Any other applicant which can make use of the properties of these compositions.

Having thus described my invention what I claim as new and desire to obtain by Letters Patent is:

1. The zwitterion reaction product formed by first reacting epichlorohydrin with an alkali metal salt of phosphorous acid, phosphoric acid, sulfurous acid or sulfuric acid to open the epoxy ring and then reacting said so-formed product containing the unreacted chlorine atom of epichlorohydrin with dimethyl dodecyl amine.

2. The zwitterion reaction product of claim 1 wherein the alkali metal salt is sodium hexametaphosphate.

References Cited by the Examiner UNITED STATES PATENTS 2,469,683 5/1949 Dudley et al 260-584 2,708,666 5/1955 Carpenter 260-309.6 2,941,003 6/1960 Shokal 260-584 2,957,003 10/1960 Johnson 260-309.6 3,017,357 1/1962 Cyba 252-32.5 3,017,362 1/1962 Cyba 2525l.5 3,029,265 4/1962 Zech 260-584 3,060,182 10/1962 Zech 260-309.6 3,201,441 8/ 1965 Petersen et al 260-978 X CHARLES B. PARKER, Primary Examiner.

NICHOLAS RIZZO, Examiner.

NATALIE TROUSOF, RICHARD L. RAYMOND,

Assistant Examiners. 

1. THE ZWITTERION REACTION PRODUCT FORMED BY FIRST REACTING EPICHLOROHYDRIN WITH AN ALKALI METAL SALT OF PHOSPHOROUS ACID, PHOSPHORIC ACID, SULFUROUS ACID OR SULFURIC ACID TO OPEN THE EPOXY RING AND THEN REACTING SAID SO-FORMED PRODUCT CONTAINING THE UNREACTED CHLORINE ATOM OF EPICHLOROHYDRIN WITH DIMETHYL DODECYL AMINE. 